Although silver is a second-row transition metal, it is often treated as an “honorary” first-row metal due to its low cost and propensity for single-electron redox chemistry, and redox catalysis with well-defined silver complexes is under-developed. While some reports of silver-catalyzed oxidation reactions in the past decade have invoked the possibility of disilver redox chemistry, and structural examples of disilver(I) complexes with commonly used ligands are plentiful, surprisingly little work has focused on understanding and utilizing the oxidation chemistry of such complexes.<br/>Here we describe a targeted investigation of the fundamental oxidation chemistry of well-defined dinuclear silver(I) complexes. Our work aims to probe the relevance of dinuclear silver complexes to nitrene transfer catalysis, through isolation and characterization of reactive intermediates; to correlate solid- and solution-state structures of silver complexes relevant to catalysis, using extended X-ray absorption fine structure (EXAFS) analysis; and, to directly interrogate silver–silver redox cooperation through stoichiometric oxidation reactions of dinuclear silver(I) complexes with carefully designed ligand sets.<br/>

Exploring dinuclear redox chemistry with silver

255th National Meeting (2018)

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